US4770750A - Process for producing transition metal powders by electrolysis in melted salt baths - Google Patents
Process for producing transition metal powders by electrolysis in melted salt baths Download PDFInfo
- Publication number
- US4770750A US4770750A US07/099,317 US9931787A US4770750A US 4770750 A US4770750 A US 4770750A US 9931787 A US9931787 A US 9931787A US 4770750 A US4770750 A US 4770750A
- Authority
- US
- United States
- Prior art keywords
- transition metal
- metal
- electrolysis
- salt bath
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 14
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 title claims abstract description 12
- 150000003839 salts Chemical class 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 230000008021 deposition Effects 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 7
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052726 zirconium Inorganic materials 0.000 claims abstract 2
- 150000004820 halides Chemical class 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 2
- 229910001508 alkali metal halide Inorganic materials 0.000 claims 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims 2
- 239000002245 particle Substances 0.000 claims 2
- 150000002739 metals Chemical class 0.000 abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000000737 periodic effect Effects 0.000 abstract description 2
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 239000007787 solid Substances 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 description 1
- 240000003259 Brassica oleracea var. botrytis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000009690 centrifugal atomisation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- -1 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
Definitions
- the present invention relates to the production of transition metal powders by the electrolysis of their halides in melted salt baths.
- Transition metals refer to any metal belonging to columns IVb, Vb, VIb of the periodic classification of elements.
- Powder is understood to mean a finely divided solid substance having grains with a size between a few fractions of a micron and approximately 200 microns.
- the process according to the present invention comprises electrolysis of a halide of the metal, particularly its chloride, dissolved in a bath of melted salts based on alkali metal or alkaline earth halides, performed under special conditions.
- Electrolytic processes which are known for these metals, lead to deposits of excellent quality from the purity standpoint and which are in the form of more or less solid or dendritic crystals, which can be directly used for melting purposes, but which are unsuitable for powder metallurgy.
- the process is characterized in that electrolysis is obtained in such a way that the deposition voltage of the metal to be obtained in powder form is 0.1 to 4.0 V and preferably 0.2 to 0.3 V below that of the alkali metal or alkaline earth metal which is the easiest to reduce.
- E of a metal from the solution of one of its salts is given by the NERNST law: ##EQU1## in which E 0 is the normal potential, R the constant of perfect gases, T the temperature in degrees K., n the number of electrons exchanged, F the FARADAY number and a the activity of the ions of the metal in the solution.
- the research carried out for realizing the invention was carried out in a cell comprising a metal tank containing the molten bath and a metal cover ensuring the sealing of the system and having a number of openings, inter alia for the tight, insulated passage of the anode and cathode devices immersed in the bath, the supply of the bath with the halide of the metal to be produced and the extraction of the halogen formed through the anode.
- the anode device also has a diaphragm subdividing the bath into two compartments, namely an anode compartment only containing traces of titanium in solution and a cathode department in which the dissolved titanium content is kept constant as a result of a continuous supply means.
- the bath is constituted by an equimolecular mixture of potassium and sodium chlorides melted at 750° C. Titanium tetrachloride is the halide introduced. Under conventional electrolysis conditions, the titanium content dissolved in the bath is 4%.
- the titanium deposition voltage measured by plotting the voltage/current curve is 2.15 V and that of the alkali which is the most difficult to reduce, i.e. in the present case sodium is 3.2 V.
- the deposits collected on the cathode are in the form of well crystallized dendrites which can reach several centimeters and comply with the following analysis in ppm:
- the electrical efficiency exceeds 85%.
- This example related to hafnium.
- the halide introduced being on this occasion hafnium tetrachloride in a quantity of 25% and under normal electrolysis conditions, i.e. with a current density of 1.0 A/cm 2 , the hafnium deposition voltage is 2.2 V and deposits are obtained in the form of relatively solid dendrites (cauliflower appearance) with an electrical efficiency exceeding 95%.
- the analysis of these deposits gives the following results in ppm:
- F-ions are introduced into the bath by adding e.g. sodium fluoride in such a way that the fluorine:hafnium molecular ratio is equal to 12, under the same electrolysis conditions the hafnium deposition voltage passes to 2.9 V and, after washing the deposit, a powder is obtained which substantially entirely passes through the 200 micron mesh size screen and complies with the following analysis in ppm:
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Length Measuring Devices By Optical Means (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8600390 | 1986-01-06 | ||
| FR8600390A FR2592664B1 (fr) | 1986-01-06 | 1986-01-06 | Procede d'elaboration de poudres de metaux de transition par electrolyse en bains de sels fondus |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4770750A true US4770750A (en) | 1988-09-13 |
Family
ID=9331054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/099,317 Expired - Fee Related US4770750A (en) | 1986-01-06 | 1987-01-05 | Process for producing transition metal powders by electrolysis in melted salt baths |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4770750A (cs) |
| EP (1) | EP0253841B1 (cs) |
| JP (1) | JPS63500187A (cs) |
| CA (1) | CA1287814C (cs) |
| DE (1) | DE3762890D1 (cs) |
| FR (1) | FR2592664B1 (cs) |
| WO (1) | WO1987004193A1 (cs) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090134038A1 (en) * | 2005-10-05 | 2009-05-28 | Tadeusz Chudoba | Method of Chemical Reactions Conduction and Chemical Reactor |
| US20110158843A1 (en) * | 2000-02-22 | 2011-06-30 | Metalysis Limited | Electrolytic reduction of metal oxides such as titanium dioxide and process applications |
| US10066308B2 (en) | 2011-12-22 | 2018-09-04 | Universal Technical Resource Services, Inc. | System and method for extraction and refining of titanium |
| US10400305B2 (en) | 2016-09-14 | 2019-09-03 | Universal Achemetal Titanium, Llc | Method for producing titanium-aluminum-vanadium alloy |
| US11959185B2 (en) | 2017-01-13 | 2024-04-16 | Universal Achemetal Titanium, Llc | Titanium master alloy for titanium-aluminum based alloys |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991001942A1 (en) * | 1989-08-01 | 1991-02-21 | Australian Copper Company Pty. Ltd. | Production of copper compounds |
| JP4688796B2 (ja) * | 2004-04-06 | 2011-05-25 | 株式会社イオックス | プラズマ誘起電解による微粒子の製造方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB736567A (en) * | 1952-07-03 | 1955-09-07 | Horizons Titanium Corp | Improvements in production of metallic titanium |
| US2951021A (en) * | 1952-03-28 | 1960-08-30 | Nat Res Corp | Electrolytic production of titanium |
| FR1265427A (fr) * | 1960-06-03 | 1961-06-30 | Ciba Geigy | Procédé d'élaboration électrolytique des métaux niobium et tantale |
-
1986
- 1986-01-06 FR FR8600390A patent/FR2592664B1/fr not_active Expired - Fee Related
-
1987
- 1987-01-05 EP EP87900658A patent/EP0253841B1/fr not_active Expired - Lifetime
- 1987-01-05 US US07/099,317 patent/US4770750A/en not_active Expired - Fee Related
- 1987-01-05 JP JP62500612A patent/JPS63500187A/ja active Granted
- 1987-01-05 CA CA000526634A patent/CA1287814C/fr not_active Expired - Lifetime
- 1987-01-05 WO PCT/FR1987/000001 patent/WO1987004193A1/fr not_active Ceased
- 1987-01-05 DE DE8787900658T patent/DE3762890D1/de not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2951021A (en) * | 1952-03-28 | 1960-08-30 | Nat Res Corp | Electrolytic production of titanium |
| GB736567A (en) * | 1952-07-03 | 1955-09-07 | Horizons Titanium Corp | Improvements in production of metallic titanium |
| FR1265427A (fr) * | 1960-06-03 | 1961-06-30 | Ciba Geigy | Procédé d'élaboration électrolytique des métaux niobium et tantale |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110158843A1 (en) * | 2000-02-22 | 2011-06-30 | Metalysis Limited | Electrolytic reduction of metal oxides such as titanium dioxide and process applications |
| US20090134038A1 (en) * | 2005-10-05 | 2009-05-28 | Tadeusz Chudoba | Method of Chemical Reactions Conduction and Chemical Reactor |
| US10066308B2 (en) | 2011-12-22 | 2018-09-04 | Universal Technical Resource Services, Inc. | System and method for extraction and refining of titanium |
| US10731264B2 (en) | 2011-12-22 | 2020-08-04 | Universal Achemetal Titanium, Llc | System and method for extraction and refining of titanium |
| US11280013B2 (en) | 2011-12-22 | 2022-03-22 | Universal Achemetal Titanium, Llc | System and method for extraction and refining of titanium |
| US10400305B2 (en) | 2016-09-14 | 2019-09-03 | Universal Achemetal Titanium, Llc | Method for producing titanium-aluminum-vanadium alloy |
| US11959185B2 (en) | 2017-01-13 | 2024-04-16 | Universal Achemetal Titanium, Llc | Titanium master alloy for titanium-aluminum based alloys |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0253841B1 (fr) | 1990-05-23 |
| JPS63500187A (ja) | 1988-01-21 |
| JPH0312156B2 (cs) | 1991-02-19 |
| CA1287814C (fr) | 1991-08-20 |
| DE3762890D1 (de) | 1990-06-28 |
| WO1987004193A1 (fr) | 1987-07-16 |
| FR2592664A1 (fr) | 1987-07-10 |
| EP0253841A1 (fr) | 1988-01-27 |
| FR2592664B1 (fr) | 1990-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4853094A (en) | Process for the electrolytic production of metals from a fused salt melt with a liquid cathode | |
| US3114685A (en) | Electrolytic production of titanium metal | |
| US2749295A (en) | Electrolytic production of titanium | |
| US4770750A (en) | Process for producing transition metal powders by electrolysis in melted salt baths | |
| US2913380A (en) | Refining titanium-vanadium alloys | |
| JPS63262492A (ja) | 金属の電解製造方法 | |
| US3137641A (en) | Electrolytic process for the production of titanium metal | |
| US4662998A (en) | Electrodeposition of refractory metal silicides | |
| US2739111A (en) | Metal production by electrolysis | |
| US2707170A (en) | Electrodeposition of titanium | |
| US2936268A (en) | Preparation of metal borides and silicides | |
| US2874454A (en) | Titanium group metals deposits | |
| Novoselova et al. | High-temperature electrochemical synthesis of carbon-containing inorganic compounds under excessive carbon dioxide pressure | |
| US2715093A (en) | Electrolytic production of molybdenum powder and coherent deposits | |
| US2939823A (en) | Electrorefining metallic titanium | |
| US2731404A (en) | Production of titanium metal | |
| US2798844A (en) | Electrolyte for titanium production | |
| US2782156A (en) | Purification of fused salt electrolytes | |
| Takenaka et al. | Dissolution and deposition of impurities in Mg electrolysis | |
| US2892762A (en) | Production of elemental boron electrolytically | |
| US3791945A (en) | Method of production of alkali metals and their alloys | |
| US4073704A (en) | Method for magnesium production using tungsten or molybdenum | |
| JPH11229172A (ja) | 高純度銅の製造方法及び製造装置 | |
| US2813069A (en) | Porous anode | |
| US2985569A (en) | Electrolytic method and means for production of refractory metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: PECHINEY, 28 RUE DE BONNEL, 69433, LYON CEDEX 03 F Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ARMAND, MARCEL;REEL/FRAME:004768/0887 Effective date: 19871008 |
|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| REMI | Maintenance fee reminder mailed | ||
| LAPS | Lapse for failure to pay maintenance fees | ||
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19960918 |
|
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |